Vitreous enamel compositions

ABSTRACT

A vitreous enamel composition comprising 1 part by weight of a vitreous enamel solid component composed of (1) 90-99.9 wt. % of glass powder consisting predominantly of 40 to 80 wt. % of SiO 2 , 1-25 wt. % of at least one of B 2  O 3  and CaO, and 1-20 wt. % of R 2  O in which R is K, Na or Li, and (2) 0.1-10 wt. % of palladium powder, and 1-20 parts by weight of an organic vehicle.

This invention relates to vitreous enamel compositions, and more particularly to vitreous enamel compositions for undercoating the glass and ceramic articles to be electrolessly plated.

Generally the surface of glass and ceramic articles can not be coated by electroless plating when subjected directly thereto. It is therefore necessary to deposit on the surface of such an article palladium, silver, gold or a derivative thereof to sensitize the surface for electroless plating. The sensitizing substance must be deposited on the surface with high adhesion and as uniformly as possible free of local irregularities. Additionally the layer of the sensitizing material should preferably be rough-surfaced to the greatest possible extent.

The surface of glass and ceramic articles is usually sensitized by applying a sensitizing material directly to the surface (to be hereinafter referred to as "direct catalyzing method"), by applying a silver paste composed of a small amount of silver powder and an organic vehicle in not more than one half the amount (by weight) of the silver and firing the resulting coating (to be hereinafter referred to as "silver past firing method"), and by applying a vitreous enamel composition composed of lead glass, an organic acid salt of sensitizing material and a small amount of organic vehicle, followed by firing (to be hereinafter referred to as "glass enamel firing method").

With the direct catalyzing method, the adhesion between the sensitizing material and the surface of the article is very low, rendering the electroless coating adhered to the article only with very low strength. According to the silver paste firing method, the electroless plating is limited only to copper plating which requires the use of large quantities of expensive silver, hence commercially very disadvantageous. The vitreous enamel firing method has the following drawbacks. Since the glass component used is lead glass which is low melting, there is an extreme limitation on the range of adjustable temperatures for forming on the surface of ceramic articles a fired layer in which the lead glass retains its particulate form. Frequently, therefore, the glass particles per se are fused, giving a smooth-surfaced vitreous layer instead of forming a porous rough surface. Moreover the glass tends to cover the sensitizing material, rendering the material less exposed, with the result that the electroless coating, if formed, will have reduced adhesion thereto.

An object of this invention is to provide a vitreous enamel composition capable of giving coatings on which platings can be formed with outstanding adhesion.

Another object of this invention is to provide a vitreous enamel composition which permits electroless deposition of nickel, cobalt and other metals as well as copper.

These and other objects of this invention will become apparent from the following description.

The vitreous enamel composition of this invention is characterized in that the composition comprises: 1 part by weight of a vitreous enamel solid component composed of (1) 90-99.9 wt. % of glass powder consisting predominantly of 40-80 wt. % of SiO₂, 1-25 wt. % of at least one of B₂ O₃ and CaO, and 1-20 wt. % of R₂ O in which R is K, Na or Li, and (2) 0.1-10 wt. % of palladium powder, and 1-20 parts by weight of an organic vehicle admixed with the solid component.

According to this invention it is essential that the vitreous enamel composition contain a glass powder consisting predominantly of 40-80 wt. % of SiO₂, 1-25 wt. % of at least one of B₂ O₃ and CaO, and 1-20 wt. % of R₂ O in which R is as defined above. The glass powder of this invention, although free from any lead component, has a relatively low melting point which is usually about 1000° to about 1250° C. and can be fired at a relatively low temperature. Moreover the powder can be fired at temperatures in a wider range than lead glass, while retaining the form of glass powder, giving a porous layer of fired glass powder on glass or ceramic articles. Since the glass powder is fired on the surface of the ceramic article, the vitreous layer can be formed as adhered thereto with high bond strength.

In this invention, the glass powder of the above composition is used conjointly with the organic vehicle in an amount of 1 to 20 times the amount by weight of the powder, the amount of the vehicle being exceedingly greater than was conventionally used in vitreous enamel compositions of this type. Consequently, a rough-surfaced layer of the glass powder can be formed uniformly on the surface of glass and ceramic articles.

The glass powder of this invention is composed preferably of 45-75 wt. % of SiO₂, 3-15 wt. % of at least one of B₂ O₃ and CaO and 5-15 wt. % of R₂ O. The composition of the glass powder is determined based mainly on the melting temperature of the glass powder, the temperature range in which the powder can be fired, the adhering properties and strength of the fired layer obtained. With less than 40 wt. % of SiO₂ present, the fired vitreous layer is liable to corrosion by the plating bath, with the result that the subsequent plating process gives metal coatings of reduced bond strength. With more than 80 wt. % of SiO₂ present, too high a firing temperature (melting temperature) will be required, adversely affecting the glass or ceramic article per se and producing a tendency to reduce the catalytic properties of the palladium powder. Further if the amount of at least one of B₂ O₃ and CaO is less than 1 wt. %, difficulty is likely to arise in melting the glass powder. Conversely if it is more than 25 wt. %, the resulting vitreous layer will have a reduced chemical stability and become susceptible to corrosion by the plating bath. Further if R₂ O is present in an amount of less than 1 wt. %, difficulty is likely to take place in melting the glass powder. With use of more than 20 wt. % of R₂ O, a reduced chemical stability and increased susceptibility to corrosion by the plating bath will result.

Insofar as the above components are used within the ranges defined above, at least one or two of BaO, MgO, NaF, ZnO, TiO₂, ZrO₂, SnO₂, Al₂ O₃, Bi₂ O₃ and Fe₂ O₃ can be used in an amount of up to 20 wt. % in this invention. Among these components, BaO and MgO act to promote vitrification, while NaF serves to adjust the melting temperature of the glass powder. ZnO, TiO₂, ZrO₂, Al₂ O₃, Fe₂ O₃, etc., are effective in giving an improved chemical stability to the glass powder.

The glass powder can be produced according to the usual method. For example, a vitreous mixture of the above composition is melted in the usual manner at 1300°-1600° C. for 1-6 hours and the molten mass is quenched in water and thereafter mechanically treated in a ball mill or the like. The resulting slurry is dried to obtain a cake, which is then pulverized by suitable means such as oscillating screen. The glass powder of this invention is usually 0.5 to 20μ, more particularly 0.5 to 10μ in particle size.

According to this invention, a palladium powder is admixed with the glass powder to obtain a vitreous enamel solid component. Useful palladium powders are finely divided metal palladium and inorganic compounds thereof, such as palladium oxide, palladium hydroxide, palladium black, etc. Palladium oxide is prepared by the usual manner, for example palladium chloride is heated with sodium nitrate at a temperature of about 600° C. Palladium hydroxide is produced by adding an aqueous solution of palladium chloride to sodium hydroxide to precipitate palladium hydroxide, removing the resulting precipitate and drying the precipitate removed. Further palladium black is prepared by dissolving palladium chloride in an aqueous solution of hydrochloric acid, adding formalin to the solution, adjusting the resulting solution to a pH of more than 7, heating the resulting alkaline solution at a temperature of 50° to 80° C. for several hours to precipitate palladium black and separating the palladium black from the solution, followed by washing with water and drying. These palladium powders are used in an amount of 0.1-10 wt. %, preferably 1-8 wt. %, based on the vitreous enamel solid component. If the proportion of the palladium powder is less than 0.1 wt. %, it is difficult to permit the formation of platings, whereas even if it is in excess of 10 wt. %, further improved results will not be achievable. The method of mixing the glass powder with the palladium powder is not particularly limited but a wide variety of methods are employable. Typically, the powders are mixed together in a mortar for at least 3 hours.

The vitreous enamel composition of this invention is prepared by diluting the glass enamel solid component with an organic vehicle in an amount of 1 to 20 times, preferably 1 to 10 times the solid component. Useful organic vehicles are those which can be evaporated off on decomposition when the vitreous enamel composition is fired. Examples are organic solvents, the mixture of water and organic solvents, and solutions or dispersions of resins in water or such solvents. Examples of organic solvents are terpene, esters, ethers, aromatic hydrocarbons, more particularly pine oil, turpentine oil, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, amyl acetate, toluene, xylene, etc. Examples of useful resins are natural and synthetic resins. Examples of useful natural resins are balsam, gum damar, copal, rosin, etc. Examples of useful synthetic resins are cellulose resin, acrylic resin, polyamide, polyester, polyvinyl acetate, polyethylene glycol, polyvinyl acetal, polyvinyl alcohol, etc. Examples of aqueous solutions or dispersions are aqueous solutions of polyvinyl alcohol, polyvinyl acetate emulsion, acryl emulsion. Also usable are organic solvent solutions or dispersions of various resins. Typical of organic vehicles are a mixture of 76 wt. % of pine oil, 6 wt. % of polyester resin (trademark; "Barnok D-161," product of Dainippon Ink and Chemicals, INC., Japan), 12 wt. % of cellulose resin (trademark; "EC-N-22," product of Hercules, U.S.A.) and 6 wt. % of polyvinyl resin (trademark: "Eslec BL-1," terpolymer of vinyl butyral, vinyl acetate and vinyl alcohol, manufactured by Sekisui Chemical Co., Japan), a mixture of 96 wt. % of pine oil and 4 wt. % of the above-mentioned cellulose resin. These vehicles are useful for preparing the vitreous enamel compositions of this invention in the form of a paste. A vehicle composed of 15 wt. % of the cellulose resin and 85 wt. % of isopropyl alcohol is well suited to the preparation of the present composition adapted for coating. Paste-like thermoplastic compositions amenable to screen printing can be prepared with use of wax-like vehicles composed of 40-60 wt. % of stearyl or cetyl alcohol and 60-40 wt. % of thermoplastic resin, such as a wax-like mixture of 40 wt. % of stearyl alcohol, 5 wt. % of polyethylene glycol (trademark: "PEG-1540," product of Sanyo Chemical Industries Co., Japan), 2 wt. % of cellulose resin ("EC-N-22"), 3 wt. % of acrylic resin (trademark: "Acrybase BM-2003," product of Fujikura Kasei Co., Japan), and 50 wt. % of corn starch.

According to this invention, a substance which will not melt during the firing of the composition can be incorporated into the composition in an amount of 1-20 wt. % based on the composition. Examples of such substances are barium sulfate, calcium sulfate kaolin, feldspar, siliceous sand, alumina, etc. The time when to add the substance is not particularly limited; for example, it may be added to the glass powder, or to the organic vehicle and the vitreous enamel solid component when the latter two are mixed together.

The vitreous enamel compositions of this invention are applicable to glass and ceramic articles by any of various usual methods. When the composition is in the form of a paste, the desired design is printed through an appropriate screen on the surface of glass and ceramic articles. Compositions adapted for coating are applied to the desired surface portion of articles by the usual method as by spraying or immersion. With compositions adapted for use with transfer paper, the design of the decalcomania can be transferred as it is. The vitreous enamel composition applied to the glass or ceramic article is then fired in the usual manner. The firing conditions are determined as desired in accordance with the composition of the vitreous enamel composition and the kind of the glass or ceramic article. Usually the firing is conducted at 550° to 900° C. for about 2 to about 30 minutes. The firing step causes the organic vehicle component to evaporate off upon decomposition, forming a layer of the glass powder containing the palladium powder on the surface of the article. Subsequently, the article is subjected to an electroless plating process in the usual manner, whereby a metal plating is formed on the glass powder layer. Prior to the electroless plating, the article can be pretreated in a simple usual manner as by being immersed in about 1-20% aqueous solution of hydrochloric acid at room temperature to about 60° C. for about 2 to about 30 minutes. For the electroless plating, a wide variety of baths are usable, typical of which are an acid or alkaline electroless nickel plating bath containing sodium hypophosfite, an electroless nickel or copper plating bath containing sodium boron hydride or like boron-type reducing agent, other usual electroless gold, silver, brass and cobalt plating baths, etc.

The vitreous enamel compositions of this invention are applicable to a wide variety of glass and ceramic articles which remain stable at the firing temperature, such as articles made of soda lime silica glass, borosilicate glass or like glass, various ceramic articles, ferites semicondutors, alumina plates etc.

The vitreous enamel compositions of this invention are readily applicable to glass and ceramic articles over the entire surface or desired portion thereof by any of the usual methods such as ordinary screen printing, transfer printing, spraying or like coating method, depending on the kind and proportion of the organic vehicle used in the composition. The composition applied to the article can be fired with ease without entailing deformation of the article itself, forming a layer with a very porous surface on which the palladium powders, i.e., the sensitizing material, are uniformly distributed as exposed over the entire surface area. Since the vitreous enamel compositions of this invention, when applied to glass or ceramic articles and fired in the usual manner, give a highly sensitized porous vitreous layer on the article integral therewith, a uniform plating of metal such as copper, nickel, cobalt, gold, silver or the like can be subsequently electrolessly formed on the article with high adhesion due to the resulting anchorage and chemical bond between the sensitizing material and the plated metal.

Thus the present invention is very useful in forming on glass and ceramic articles decorative or colored metal coatings with high durability. The vitreous enamel compositions of this invention are useful also for glazing glassware and ceramic ware because of their outstanding resistance to acids and alkalis.

This invention will be described below with reference to examples, in which the percentages are all by weight.

EXAMPLE 1

A vitreous mixture of the following composition is prepared.

    ______________________________________                                                             %                                                          ______________________________________                                                 SiO.sub.2     72.0                                                             CaO           9.6                                                              MgO           4.4                                                              Na.sub.2 O    13.0                                                             Al.sub.2 O.sub.3                                                                             1.0                                                      ______________________________________                                    

The mixture is fused at 1400° C. in an electric furnace and then quenched in water to obtain a vitreous frit. The wet frit is ground in a pot mill for 4 days to prepare a slurry, which is dried and thereafter comminuted on a 200-mesh oscillating screen to obtain a glass powder according to this invention. The glass powder has a coefficient of expansion of 96×10⁻⁷ cm/cm/°C. and particle-size distribution of: 34.2% of smaller than 2μ, 36.0% of 2-4μ, 17.0% of 4-6μ, 9.7% of 6-8μ, and 3.1% of larger than 8μ.

On the other hand, palladium chloride is dissolved in an aqueous solution of hydrochloric acid, formalin is added to the solution, and the resulting solution is adjusted to a pH of about 8 with sodium hydroxide. The solution is heated at 80° C. for 1 hour, and the palladium black separated out is filtered off, washed with water and spontaneously dried to obtain a palladium powder.

A 940 g portion of the glass powder and a 60 g portion of the palladium powder obtained as above are mixed together in a mortar for 5 hours. An oil serving as an organic vehicle and composed of 96% of pine oil and 4% of cellulose resin (trademark: "EC-N-22," product of Hercules INC.) is added to the mixture in three times the amount by weight of the solids of the mixture. The resulting mixture is kneaded for 5 hours, and the paste obtained is further treated with three rollers to prepare a uniform vitreous enamel composition of this invention.

The vitreous enamel composition is printed, in an amount of 0.005 g/cm², on a fired pure alumina plate through a 200-mesh screen. The printed plate is placed into a box furnace the internal temperature of which is thereafter raised at a rate of 40° C./min. The composition is fired at 630°±10° C. for 10 minutes.

The vitreous enamel test piece thus prepared is immersed in a 10% solution of hydrochloric acid at 50° C. for 10 minutes for pre-treatment and is subsequently electrolessly plated in a five-fold dilution of "Acid type Chemical Nickel Plating Solution," product of Okuno Chemical Industry Co. at 90° C. for 10 minutes to form a uniform nickel plating on the test piece. The plating is held adhered to the fired alumina plate with bond strength of as high as 0.7 kg/mm². The bond strength is measured by soldering a copper wire 0.5 mm in diameter to the nickel plating and pulling the copper wire at right angles to the plate on a tension tester (product of Shimazu Seisakusho Co., Ltd., Japan).

EXAMPLE 2

A vitreous mixture of the following composition is prepared.

    ______________________________________                                                             %                                                          ______________________________________                                                 SiO.sub.2     60                                                               B.sub.2 O.sub.3                                                                              7                                                                Al.sub.2 O.sub.3                                                                             5                                                                Na.sub.2 O    14                                                               ZrO           5                                                                TiO.sub.2     9                                                        ______________________________________                                    

The mixture is fused at 1500° C. in an electric furnace and then quenched in water to obtain a vitreous frit. The wet frit is ground in a pot mill for 4 days to prepare a slurry, which is dried and thereafter comminuted on a 200-mesh oscillating screen to obtain a glass powder according to this invention.

The glass powder and the palladium powder obtained in Example 1 are mixed together in the specified proportions shown in Table 1. The organic vehicle disclosed below is added to the mixture in two times the amount by weight of the solid of the mixture, and the resulting mixture is kneaded for 5 hours to obtain vitreous enamel compositions.

    ______________________________________                                         Organic vehicle:          %                                                    ______________________________________                                         Pine oil                  80                                                   Cellulose resin as shown in                                                     Example 1                15                                                   Polyvinyl acetal ("Eslec BL-1                                                   product of Sekisui Chemical Co.)                                                                        5                                                    ______________________________________                                    

The vitreous enamel composition is printed, in an amount of 0.005 g/cm², on a fired pure alumina plate through a 300-mesh screen. The printed plate is placed into a box furnace the internal temperature of which is thereafter raised at a rate of 30° C./min. The composition is fired at 740°±10° C. for 15 minutes.

The vitreous enamel test piece thus prepared is immersed in a 10% solution of hydrochloric acid at 45° C. for 15 minutes for pre-treatment and is subsequently electrolessly plated in an electroless plating bath composed of 1000 ml of "Sylek #202" (product of du Pont) and 28 ml of "Sylek #222" (product of du Pont). The resulting piece thus plated is checked for the following plating properties. The results are given in Table 1 below.

                                      Table 1                                      __________________________________________________________________________     No.                    1  2  3  4  5                                           __________________________________________________________________________     Proportions of glass                                                                       glass powder (%)                                                                          99.95                                                                             99.8                                                                              95.0                                                                              90.0                                                                              87.0                                        powder and Palladium                                                                       Palladium Powder                                                                          0.05                                                                              0.2                                                                               5.0                                                                               10.0                                                                              13.0                                        powder                                                                         Plated area (%)        10 100                                                                               100                                                                               100                                                                               100                                         Bond strength          0.8                                                                               1.2                                                                               1.8                                                                               1.8                                                                               1.7                                          (Kg/mm.sup.2)                                                                 __________________________________________________________________________

The above bond strength is measured in the same manner as in Example 1.

EXAMPLE 3

A vitreous mixture of the following composition is prepared.

    ______________________________________                                                             %                                                          ______________________________________                                                 SiO.sub.2     72.0                                                             CaO           9.6                                                              MgO           4.4                                                              Al.sub.2 O.sub.3                                                                             1.0                                                              Na.sub.2 O    13.0                                                     ______________________________________                                    

The glass powder according to this invention is prepared in the same manner as in Example 2 from the above vitreous mixture.

74 parts by weight of glass powder, 20 parts by weight of alumina and 6 parts by weight of palladium oxide are mixed together in a mortar for 5 hours. The same organic vehicle as in Example 2 is added to the mixture in the specified proportions disclosed in Table 2 and the resulting mixture is kneaded for 5 hours to obtain vitreous enamel compostions.

The vitreous enamel composition is printed, in an amount of 0.005 g/cm², on a fired pure alumina plate through a 300-mesh screen. The printed plate is placed into a box furnace the internal temperature of which is thereafter raised at a rate of 30° C./min. The composition is fired at 660°±10° C. for 15 minutes.

The vitreous enamel test piece thus prepared is immersed in a 10% solution of hydrochloric acid at 50° C. for 15 minutes and subsequently in a 20% solution of sodium hypophosphite at 85° C. for 5 minutes for pretreatment. The pre-treated piece is then electrolessly plated in an electroless plating bath ("TMP," Chemical Copper Plating Solution, product of Okuno Chemical Industry Co., Japan) composed of 1 part by volume of A-type, 1 part by volume of B-type and 4 parts by volume of water at 25° C. for 15 minutes. The resulting piece thus plated is checked for the following plating properties. The results are given in Table 2 below.

                  Table 2                                                          ______________________________________                                         No.           1       2       3     4    5                                     ______________________________________                                         Proportions of solid                                                           component and organic                                                                        1/0.2   1/2     1/7   1/15 1/25                                  vehicle                                                                        Plated area (%)                                                                              20      100     100   100  70                                    Bond strength (kg/mm.sup.2)                                                                  0.1     2.0     1.8   1.0  0.05                                  ______________________________________                                     

What is claimed is:
 1. A vitreous enamel composition for undercoating glass and ceramic articles to be electrolessly plated comprising 1 part by weight of a vitreous enamel solid component composed of(1) 90-99.9 wt. % of glass powder consisting of 40 to 80 wt. % of SiO₂, 1-25 wt. % of at least one of B₂ O₃ and CaO, 1-20 wt. % of R₂ O in which R is K, Na, or Li and up to 20 wt. % of at least one of BaO, MgO, NaF, ZnO, TiO₂, ZrO₂, SnO₂, Al₂ O₃, Bi₂ O₃ and Fe₂ O₃, and (2) 0.1-10 wt. % of palladium powder, and 1-20 parts by weight of an organic vehicle.
 2. The vitreous enamel composition according to claim 1, in which said glass powder consists of 45-75 wt. % of SiO₂, 3-15 wt. % of at least one of B₂ O₃ and CaO, and 5-15 wt. % of R₂ O in which R is K, Na or Li.
 3. The vitreous enamel composition according to claim 1, in which said vitreous enamel solid component is composed of (1) 92-99 wt. % of glass powder consisting of 40 to 80 wt. % of SiO₂, 1-25 wt. % of at least one of B₂ O₃ and CaO, and 1-20 wt. % of R₂ O in which R is K, Na or Li, and (2) 1 to 8 wt. % of palladium powder.
 4. The vitreous enamel composition according to claim 1, in which said organic vehicle is contained in an amount of 1-10 parts by weight based on 1 part by weight of the vitreous enamel solid component.
 5. The vitreous enamel composition according to claim 1 which further contains at least one of substances not melting during firing of the composition.
 6. The vitreous enamel composition according to claim 5, in which said substance is at least one of barium sulfate, calcium sulfate, kaolin, feldspar, siliceous sand and alumina. 